Halogenated bicycloheptenyl compounds as insecticides

ABSTRACT

A METHOD OF CONTROLLING INSECTS IS DESCRIBED BY APPLYING TO TH LOCUS OF THE INSECTS TO BE TREATED AN INSECTICIDAL AMOUNT OF A COMPOSITION OF THE STRUCTURE   1,2,3,4,7,7-HEXA(X-),5-(X-CH2-),6-(R-COO-CH2-)-   2-NORBORNENE   WHEREIN R IS SLECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL, HETEROCYCLIC   (1,2,3,4,7,7-HEXA(X-),5-(X-CH2-)-2-NORBORNEN-6-YL)-   CH2-CO-ALKYLENE- AND   (1,2,3,4,7,7-HEXA(X-)-2-NORBORNEN-6-YL)-CH2-OOC-   AND X IS HALOGEN SLEECTED FROM THE GROUP CONSISTING OF CHLORINE, FLOURINE AND BROMINE. THE COMPOUNDS ARE PREPARED BY REACTING AND ACYL HALIDE R-CO-X WITH 4,5,6,7,8,8-HEXAHALO-3A, 4,7,7A-TETRAHYDRO-4,7METHANOPHTHALAN IN THE PRESENCE OF A FRIEDEL CRAFTS CATALYST.

United States 3,629,421 HALOGENATED BICYCLOHEPTENYL COM- POUNDS AS INSECTICIDES Sheldon B. Greenbaum, Tonawanda, Samuel Gelfand, Niagara Falls, and Edward D. Weil, Yonkers, N.Y., assignors to Hooker Chemical Corporation, Niagara Falls, N.Y.

No Drawing. Division of application Ser. No. 533,847, Mar. 14, 1966. Continuation-impart of application Ser. No. 142,514, Oct. 3, 1961. This application Jan. 1, 1969, Ser. No. 807,150

Int. Cl. A01n 9/00, 9/22 U.S. Cl. 424263 2 Claims ABSTRACT OF THE DISCLOSURE A method of controlling insects is described by applying to the locus of the insects to be treated an insecticidal amount of a composition of the structure X i X/' 011,00 R

X CH X wherein R is selected from the group consisting of alkyl, aryl, heterocyclic and X is a halogen selected from the group consisting of chlorine, fluorine and bromine.

The compounds are prepared by reacting an acyl halide and 1 (BOX) with 4,5,6,7,8,8 hexahalo 3a,4,7,7a tetrahydro-4,7 methanophthalan in the presence of a Friedel Crafts catalyst.

atent O 3,629,421 Patented Dec. 21, 1971 their chlorinated products containing one to four atoms of chlorine. The esters are of the structure:

wherein X is a halogen, the same or different and R is chosen from the group consisting of alkyl, aryl, heterocyclic,

The alkyl group is preferably of 1 to 18 carbon atoms, more preferably of 1 to 4 carbon atoms. The aryl group may be naphthalenic but is preferably mononuclear and of 6 to 18 carbon atoms. When R is heterocyclic, it is preferably of 4 to 18 carbons and the heterocyclic ring preferably contains only either nitrogen, oxygen or phosphorus, in addition to carbon. The alkylene group of is preferably of 1 to 8 carbon atoms. substituents which may be on the various radicals, R, include the halogens, preferably chlorine or bromine, alkyl groups, preferably of l to 8 carbon atoms, phenyl, chlorophenyl and bromo phenyl, and other non-interfering substituents from the group of nitro-, amino-, nitrilo-, lower alkoxy, lower phenoxy and lower alkenyl. Preferably R will be either unsubstituted or monosubstituted but polysubstitution, up to about 4 substituents is also within the invention.

Illustrative examples of the compounds of this invention include but are not limited to the following:

2-chloromethyl-1,4,5,6,7,7-hexachlorobicyclo-(2.2.1

hept-5-en-3-y1methyl acetate;

2-chloromethyl-1,4,5,6,7,7-hexabromobicyclo- (2.2.1

hept-S-en-B-ylmethyl acetate;

2-chloromethy1-l,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-

hept-5-en-3-ylmethyl propionate;

2-chloromethyll ,4,5 ,6,7,7-hexachlorobicyclo- 2.2.1 hexachlorobicyclo- 2.2.1 -hept-5-en-3-ylmethyl butyrate;

2-chloromethyl-1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-

hept-5-en-3-ylmethyl valerate;

. Z-chloromethyl-1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-

hept-5-en-3-ylmethyl hexanoate; 2-chlorornethyl-1 ,4,5,6,7,7-hexachlorobicyc1o- (2.2.1

hept-5-en-3-ylmethyl decanoate; 2-chloromethyl-l,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-

hept-S-en-3-ylmethyl stearate; 2-chloromethyl-1,4,5,6,7,7-hexachlorobicyclo-(2.2.1

hept-S-en-3-ylmethyl benzoate; 2-chloromethyl-1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-

hept-5-en-3-ylmethyl furoate; 2-chloromethyl-1,4,5,6,7,7-hexachlorobicyclo-(2.2.1

hept-5-en-3-ylmethyl picolinate;

3 2-chloromethyl-1 ,4,5,6,7,7-hexachlorobicyclo- 2.2.1

hept-5-en-3-ylmethyl oxalate; 2-chloromethyl-1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-

hept-5-en-3-ylmethyl malonate; 2-chloromethyl-1,4,5 ,6,7 ,7-hexachlorobicyclo-( 2.2.1

hept-5-en-3-ylmethyl succinate and 2-chloromethyl-l,4,5 ,6,7,7-hexachlorobicyclo-( 2.2.1

hept-5-en-3-ylmethyl adipate.

In thei-r composition aspect the products of this invention offer several advantages of commercial significance. For example, the ester products and particularly, the chlorinated ester products of this application are extremely potent contact insecticides against a variety of crawling and flying insects including the housefly, mosquito, cockroaches, ants, spiders, beetles, thrips and grasshoppers, among many others. Since it is well known that insects are among the important carriers or vectors of infection and disease, an insecticide having a broad spectrum of insecticidal activity such as the inventive composition are especially valuable from a public health standpoint.

That the compositions of this invention are pesticidally active at all is most surprising in view of the inactivity of closely related compounds possessing the two groups sans a chloromethyl (CH Cl). For example, the structure:

is inactive but where one group of is replaced by CH CI, the compounds show good activity as a contact insecticide. As stated, infra, further chlorination substantially enhances the contact activity of the product.

Ancillary but important advantages of the novel products of this invention are long insecticidal persistence, rapid action and relative innocuousness to mammals, as well as lack of phytotoxicity.

An additional advantage of the products of this invention is the variety of formulations in which they may be utilized for insecticidal use. For example, the products purified or crude may be combined with other biocides or pesticides, including insecticides, such as DDT, methoxychor, lindane, aldin, endrin, DDD, BHC, parathion, malathion, methyl parathion, lead arsenate, calcium arsenate, rotenone, allethrin, pyrethrum, nicotine, summer oils, dormant oils, dinitroalkylphenols, dinitrocresols, chlordane, heptachlor, insecticidal carbamates and organophosphates; chlorinated terpenes, dimeton, thiophosphates and dithiophosphates such as Guthion, Diazinon, Dibrom and others; miticides such as bis(pentachlorocyclopentadienyl), chlorinated arylsulfonates, chlorinated diarylsulfones, and the like, fungicides such as sulfur, dithiocarbamates and N-trichloromethylthio-4-cyclohexene- 1,2-dicarboximide to list but a few.

It may also be desirable to combine the insecticidal products of this invention with a class of potentiators or synergists known in the insecticidal art as knockdown agents. These substances are insecticides which when combined with other insecticides will shorten the time required, or reduce the amount of the insecticide necessary to effect total immobilization (knockdown) or death of the insect to be controlled. Among the large number of synergists which may be used for this purpose are the organic thiocyanates and the water soluble organophos- 4 phates, such as phosdrin, and Sesoxane (2,3,4-methylenedioxphenoxy)-3,6,9-trioxaundocane, to name :but a few.

Another advantage of the inventive compositions is that they may readily be formulated as solids or liquids using solid or liquid solvent vehicles, carriers or extenders.

Suitable diluents are solids or liquids of an inert nature. Illustrative solid diluents include among many others: sawdust, clay, talcs, flours, silicas, alkaline earth carbonates, oxides and phosphates, sulfur and the like.

Suitable solvents for liquid formulations include water, ketones, alcohols, aromatic and aliphatic hydrocarbons and petroleum fractions or distillates.

Whether dissolved or dispersed, suspended or emulsified in a liquid or formulated as a dust or powder or some other solid preparation the insecticides of this invention may advantageously contain one or more substances known or referred to variously as modifiers, wetting agents, surface active agents, dispersing agents, suspending agents, emulsifying agents or conditioning agents, said materials being referred to herein generically as adjuvants. Thus, any substance which facilitates formulation, handling and application of the insecticide of this invention may be profitably incorporated in the insecticidal composition. Frequently, said adjuvants enhance or potentiate insecticidal effectiveness. A satisfactory but not exhaustive list of these substances appears among other places in Soap and Chemical Specialties, volume 31, pages 50-61; No. 8, pages 48-61; No. 9, pages 52-67 and No. 10, pages 38-67 (1955). Another excellent source of this information is Bulletin E-607 of the Bureau of Entymology and Plant Quarantine of the United States Department of Agriculture.

The insecticidal compositions of this invention may be applied as a dust or a spray using among other things, any of the above-mentioned exemplified formulations.

The preferred method of application is a spray using petroleum fractions or distillates as diluents plus one or more conditioning agents as formulation adjuvants. Ordinarily, a typical spray will contain between 0.001 and ten percent by weight of insecticide with the remaining material being made up largely by solvent with a small amount of adjuvant.

In its process aspects, this invention offers the advantage of two different economically feasible processes for preparing the compositions of this invention in good yield by one step processes using commercially available starting materials. The first process is to heata solution of equimolar quantities of 4,5,6,7,8, 8-hexahalo-3a,4,7,7atetrahydro-4,7-methanophthalan and the appropriate aliphatic, aromatic or heterocyclic acid chloride in the presence of a catalyst such as ZnCl AlCl BF or FeCl The reaction is set forth below:

I CH2 x X i catalyst X i CHZOGR CXz O RCOX I 0X2 .X X CH X \l/ l/ 2 wherein X is halogen, the same or different and R is chosen from the group consisting of alkyl, aryl and heterocyclic, as described before. I

The above reaction proceeds at relatively wide ranges of temperatures, minus ten degrees to plus two hundred and fifty degrees centigrade, depending upon the reactivity of the acid chloride. However, satisfactory yields can be obtained even at somewhat lower and higher temperatures if the reaction time can be proportionately raised or lowered. Where both reactants are liquids, it is possible to run the reaction without using a diluent, although a diluent such as an inert aromatic or aliphatic hydrocarbon makes for a smoother reaction. After the reactants have been allowed to react with vigorous stirring for one to eight hours, the heat source is removed and the reaction mixture is allowed to cool to room temperature and remain at this temperature for one to three hours. At this point, the ester product is distilled off (if a liquid), or fractionally crystallized, if a solid.

An alternative preparation is to heat equimolar quantities of a hexahalocyclopentadiene and a 1-acyloxy-4- halobutene-2 to a temperature of between one hundred and twenty to one hundred and eighty degrees centigrade, preferably about one hundred and fifty to one hundred and sixty degrees centigrade for a period of thirty to eighty hours depending upon the reactivity of the reactants. Again depending upon the physical characteristics of the product, distillation or crystallization is used to separate and purify the products from by-products, diluents and catalysts. The alternative process is as follows:

1 n-o-omob-n x l CHr-OC-R HC-CHzX OX2 pirical observations, it is believed that the initial one or two atoms of chlorine are taken up on the -CH groups of the ester linkage to produce CHC1-O or CCl O groups. A more'detailed discussion of the chlorination process and products appear in the examples which follow.

EXAMPLE 1 Preparation of Z-chloromethyl-1,4,5,6,7,7-hexachlorov bicycle-(2.2. 1 -hept--en-3-ylmethyl benzoate A mixture of thirty-four grams of 4,5,6,7,8,8-hexachloro chloro 3a,4,7,7a. tetrahydro 4,7 methanophthalan, fourteen grams of benzoyl chloride and one gram of zinc chloride is heated at two hundred and eight to two hundred and twenty degrees centigrade for 1.25 hours. After standing overnight, the viscous syrup is dissolved in n hexane, freed of insoluble matter bl filtration and crystallized by cooling. The crystalline product melts at one hundred and twenty-two to one hundred and twenty-four degrees centigrade. Infrared analysis confirms the presence of the described benzoyl ester. When, in place of 'benzoyl chloride, other suitable aryl chlorides, such as chloro or lower alkyl-substituted aroyl, e.g. benzoyl chlorides, are used, corresponding esters are made.

Analysis.-Calculated for C H O Cl (percent): Cl, 51.3. Found (percent): Cl. 51.5.

EXAMPLE 2 Chlorination of the product of Example 1 Solutions containing 24.2 grams of the product of Example 1 dissolved in one hundred milliliters of carbon tetrachloride are treated with elementary chlorine at sixty to seventy degrees centigrade in the presence of ultraviolet light. The chlorinations are conducted so as to afford 1,2,3 and 4 moles of reacted chlorine per mole of starting material. In each case, the progress of the chlorination is followed by titration of the hydrogen chloride released into a suitable trap. After a nitrogen purge, the solvent is removed under reduced pressure and this affords a series of the desired chlorinated products as viscous yellow oils designated as A, B, C and D.

Preparation of Z-chloromethyl-l,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-hept-5-en-3-ylmethyl acetate (A) Cis-2 butene-1,4-chlorohydrin is prepared as follows: one kilogram of cis-2-butene-1,4-diol is dissolved in a mixture of 1.29 liters of triethylamine and 1.75 liters of anhydrous ether. The mixture is stirred and treated with eight hundred and two milliliters of thionyl chloride at minus five to five degrees centigrade over two and one-half hours. The triethylamine hydrochloride is removed, washed with benzene, and the washings and filtrate are poured onto this with vigorous stirring. The organic layer is removed and dried over magnesium sulfate. Distillation through a packed column gives a cut distilling at seventy-three to seventy-six degrees centigrade/ten to thirteen millimeters, n 1.4793, which is taken as the desired chlorohydrin.

(B) Preparation of 2-butene-1,4-chlorohydrin monoacetate: 53.5 grams of Z-butene-1,4-chlorohydrin and sixty grams of triethylamine are dissolved in three hundred milliliters of dry toluene. 47.2 grams of acetyl chloride dissolved in one hundred and fifty milliliters of toluene is added over a period of one hour at zero plus or minus five degrees centigrade with stirring. The mixture is then allowed to warm up and stir at room temperature for two additional hours. Removal of the triethylamine hydrochloride gives a filtrate which is fractionated to give the desired product boiling at ninety-five degrees centigrade/twenty-six to twenty-eight millimeters.

(C) Reaction of hexachlorocyclopentadiene with 2- butene-1,4-chlorohydrin monoacetate: A mixture of 7.5 grams of 2-butene-1,4-chlorohydrin monoacetate and 13.5 grams of hexachlorocyclopentadiene is heated to one hundred and fifty degrees centigrade for forty hours. The mixture is then stripped of solvent and fractionated. The desired product, 2 chloromethyl 1,4,5,6,7,7 hexachlorobicycle (2.2.1) hept 5 en-3-ylmethyl acetate, distills at one hundred and forty-five to one hundred and forty-eight degrees centigrade/ 0.25 millimeter (13.0 grams). Similar useful products are made by using 2- butene-1,4-chlorohydrin mono-lower alkanoates, such as the lower propionate, hexanoate or decanoate.

Analysis.Calculated for CnHgOgClq (percent): Cl, 58.9. Found (percent): Cl, 59.5.

EXAMPLE 4 Chlorination of product of Example 3 with one mole of chlorine 19.5 grams of the product of Example 3 is dissolved in one hundred milliliters of carbon tetrachloride and treated with gaseous chlorine at sixty to seventy degrees centigrade. The progress of the reaction is followed by titration of the hydrogen chloride released into a trap. When one equivalent of hydrogen chloride per mole of compound is obtained, the reaction is stopped and the solvent removed under reduced pressure. The final product is the desired chlorinated reactant, obtained as a viscous, yellow oil.

EXAMPLE 5 Preparation of 2-chloromethyl-1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-hept5-en-3-ylrnethyl (4-nitrobenzo-ate) 9.3 grams of p-nitrobenzoyl chloride, 1.1 gram of 4,5,6,7,8,8 hexachloro 3a,4,7,7a tetrahydromethanophthalan and 0.5 grams of anhydrous zinc chloride are heated to two hundred degrees centigrade for one hour and then to two hundred and forty degrees centigrade for an additional two hours. After cooling, the mixture is extracted with hexane. Evaporation of the solvent and recrystallization of the residue from ethanol give the product in the form of crystals melting at one hundred and twenty-three to one hundred and twenty-six degrees centigrade. By using other suitable substituted benzoyl chlorides such as methylor chlorobenzoyl chlorides, corresponding desirable products are obtained.

Analysis.Calculated for C H NO CI (percent): N, 2.68. Found (percent): N, 2.64.

EXAMPLE 6 Insecticidal testing of products of this invention on housefiies Fifty adult housefiies of the Chemical Manufacturers Association strain are sprayed with aqueous dispersions of the test chemical at various concentrations in a two by five inch diameter stainless steel cage faced on top and bottom with fourteen mesh screen. The flies are retained in the cage in which they are sprayed for knockdown twenty-four observations and mortality determination.

Percent knockdown Percent kill Concentration Concentration Preparation from example 1 percent 0.1 percent 1 percent 0.1 percent Although the present invention has been described in terms of certain embodiments or examples, it is not intended that this invention be limited by these embodiments or examples except as indicated by the following claims.

We claim:

1. A method of controlling insects comprising applying to the locus of the insects to be treated an insecticidial amount of a compound of the structure wherein R is selected from the group consisting of. alkyl of 1 to 18 carbon atoms, phenyl, nitro phenyl, chlorophenyl, bromophenyl, furyl, pyridyl, naphthyl,

and chlorinated products thereof containing from 1 to 4 additional chlorine atoms per molecule; and X is a halogen selected from the group consisting of chlorine, bromine and fluorine.

2. The method of controlling insects comprising applying to the locus of the insects to be controlled an insecticidal amount of the compound obtained by chlorinating an ester of 2-halomethyl-3-substituted bicycloheptene-S of the structure;

wherein R is selected from the group consisting of alkyl of 1 to 18 carbon atoms, phenyl, nitro phenyl, chlorophenyl, bromophenyl, furyl, pyridyl, naphthyl,

o X 0 X -a1k 1ene-ii-oonz I li-o-om l X :I\ X2 and X2 XCH3 I X XGH I X 5/1967 Taylor 424263 ALBERT T. MEYERS, Primary Examiner J. D. GOLDBERG, Assistant Examiner US. Cl. X.R.

fzg gg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIQN Patent No. 3, 9,'+ Dated December 2l, l97l inventor) SheLdon a. Greenbaum, Samuel Gelfand 5 Edward 0; Neil It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

O I q Column 1, line 35, that portion of the formula reading H I ll -alkylene-C-CH should read -alkylene-C-O-CH Column 2, line 30, that portion of the formula reading y I a u -alkylene-C-OCH should read 1-alkylene-C-OCH Column 3, l ine 3 0, the left hand portion of the formula reading T Cl Cl should appear as c Cl Cl Cl Column 5, line 20, the left hand portion of the equation should be corrected by inserting between the two formulae; line 50 "bl" should read ---by---. Column 6, line "HCl" should read ---HCl/-; line 53, "this" should read ---ice---; line 27, "13793" should read "-1. 739""o Signed and sealed this 13th day of June 1972.

(SEAL) Attest:

EDWARD M. FLETCHER,JR Attesting Officer Commission-ewe f" Patents. 

